Cement compositions containing coarse barite, process for making same and methods of cementing in a subterranean formation

ABSTRACT

Cement comprising barite, a process for preparing such cement, and methods of cementing in a subterranean formation or well bore using such cement are provided. The cement is prepared by introducing coarse barite to the cement, the course barite comprising particles having a particle size primarily greater than about 125 microns. The presence of the coarse barite in the cement causes the cement to have a relatively low viscosity. Introducing the barite to the cement also increases the density of the cement, thus rendering the cement capable of controlling high hydrostatic pressures in a well bore.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Continuation Application claiming priority to U.S. patentapplication Ser. No. 10/324,523, filed Dec. 19, 2002 and entitled“Cement Compositions Containing Coarse Barite, Process For Making Sameand Methods of Cementing in a Subterranean Formation,” which isincorporated by reference herein in its entirety.

FIELD OF THE INVENTION

This invention generally relates to cementing in a subterraneanformation or well bore. More specifically, the invention relates to acement comprising coarse barite and a process for making the same.

BACKGROUND OF THE INVENTION

Well cementing is a process used in penetrating subterranean zones (alsoknown as subterranean formations) to recover subterranean resources suchas gas, oil, minerals, and water. In well cementing, a well bore isdrilled while a drilling fluid is circulated through the well bore. Thecirculation of the drilling fluid is then terminated, and a string ofpipe, e.g., casing, is run in the well bore. The drilling fluid in thewell bore is conditioned by circulating it downwardly through theinterior of the pipe and upwardly through the annulus, which is locatedbetween the exterior of the pipe and the walls of the well bore. Next,primary cementing is typically performed whereby a slurry of cement andwater is placed in the annulus and permitted to set into a hard mass(i.e., sheath) to thereby attach the string of pipe to the walls of thewell bore and seal the annulus. Subsequent secondary cementingoperations, e.g., completion and work over operations, may also beperformed.

In some situations, the cement slurry is subjected to relatively highhydrostatic pressures in the well bore. As such, the density of thecement slurry needs to be sufficiently high to ensure that the cementcan contain such high pressures. However, the density of conventionalcement slurries containing Portland cement and water is often less thandesired. One method developed for overcoming this limitation ofconventional cement slurries is to increase the slurry density by addinga weighting material to the slurry. A weighting material is a materialhaving a specific gravity higher than that of the other components inthe slurry such as the Portland cement, which typically has a specificgravity in the range of 3.15 to 3.2. Commonly employed weightingmaterials are iron oxide (i.e., hematite) and manganese oxide (i.e.,hausmannite). Hematite and hausmannite are commercially available fromHalliburton Energy Services, Inc. under the trade names HI-DENSE® NO. 4and MICROMAX, respectively, and they have an average specific gravity of5.2 and 4.9, respectively.

In some situations, the weighting material is soluble in and thus canhave an adverse effect on certain fluids in the well bore. For example,the high concentrations of soluble metal salts, such as those containingiron and manganese, in hematite and hausmannite, respectively, cancontaminate certain types of brines used in completion and work overcementing operations. The presence of some weighting materials in acement slurry also can undesirably cause the slurry to have a relativelyhigh viscosity. Thus, the ability to pump the cement slurry into thewell bore may be compromised by the use of the weighting material. Aneed therefore exists to develop a process for increasing the density ofa cement slurry without risking contamination of fluids in the well boreand without compromising the ability of the slurry to be pumped. Thepresent invention utilizes a new weighting material that does notadversely affect fluids in the well bore to form a pumpable cementslurry having a relatively high density.

SUMMARY OF THE INVENTION

The present invention includes cement comprising barite, a process forpreparing such cement, and a methods of cementing in subterraneanformations and well bores using such cement. The cement is prepared byintroducing coarse barite, i.e., barite comprising particles having aparticle size primarily greater than about 125 micrometers (microns), tothe cement. Preferably, 90 percent of the barite particles is greaterthan about 125 microns in size. The presence of the coarse barite in thecement causes the cement to have a relatively low viscosity. As such,the cement can be mixed with a fluid to form a pumpable slurry that canbe pumped into a well bore during well cementing. Introducing the bariteto the cement also increases the density of cement, thus rendering thecement capable of controlling hydrostatic pressures in a well bore.

DESCRIPTION OF THE DRAWINGS

The invention, together with further advantages thereof, may best beunderstood by reference to the following description taken inconjunction with the accompanying drawing in which:

FIG. 1 illustrates the particle size distribution of a preferred coursebarite for use with the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In preferred embodiments, coarse barite is introduced to a cement toreduce its density. Barite is a common name for BaSO₄, i.e., bariumsulfate. Barite that is added to drilling fluids during wellboreconstruction is generally manufactured by the guidelines set forth inAmerican Petroleum Institute (API) Specification 13A, FourteenthEdition, Aug. 1, 1991. This specification provides chemical and physicalmanufacturing requirements for barite to be used in drilling fluids. Asused herein, coarse barite refers to barite, typically subjected to acrushing and screening process, having a particle size primarily greaterthan about 125 microns. Because the coarse barite has a relatively highspecific gravity in the range of from about 4 to about 4.25, it servesas a weighting material that increases the density of the cement to inthe range of from about 15 pounds (lbs)/gallon (gal) to about 23lbs/gal, preferably from about 16 lbs/gal to about 21 lbs/gal, and morepreferably from about 17 lbs/gal to about 20 lbs/gal. The viscosity ofthe resulting cement slurry depends on many factors, one of which is theaverage particle size distribution (PSD) of the barite. In particular, alarger PSD results in a lower slurry viscosity due to the smallersurface area associated with fewer particles. As such, the cement slurrycontaining the coarse barite is sufficiently viscous to be pumped into awell bore. Reducing rheologies in this manner is generally desirable,barring sacrificing of stability control. The coarse barite may also beused to marginally increase the thickening time of the slurry.

In some embodiments, the cement composition is prepared by first dryblending the coarse barite with any known cement. The cement may be anyhydraulic cement composed of various species containing calcium,aluminum, silicon, oxygen, and/or sulfur which sets and hardens byreaction with water. Examples of suitable hydraulic cements are Portlandcements, pozzolanic cements, gypsum cements, high alumina contentcements, silica cements, and high alkalinity cements. The cement ispreferably a Portland cement, more preferably a class A, B, C, G, or HPortland cement, and most preferably a class G or H Portland cement. Asuitable coarse barite is commercially available from Halliburton EnergyServices, Inc. (hereinafter “HES”) under the tradename SWEEP-WATE™. Thisparticular form of barite is coarsely ground such that about 90% of thebarite particles have a particle size greater than about 125 microns. Apreferred particle size distribution of the barite is shown in FIG. 1.In particular, FIG. 1 depicts the particle size distribution ofSWEEP-WATE™ barite. The mean particle diameter and median particlediameter of SWEEP-WATE™ barite are about 305 microns and about 289microns, respectively. Its specific surface area is about 4,566 cm²/mL.As used herein, the symbol “%” represents the term “percent”. The amountof coarse barite added to the cement can vary depending on the desireddensity of the cement slurry. For example, the amount of barite added tothe cement may range from about 5% to about 100% by weight of thecement, more preferably from about 10% to about 70%, and yet morepreferably from about 15% to about 50%.

The resulting cement/barite blend can be stored until it is desirable toplace the blend in a well bore, at which point it can be transported tothe location of the well bore. A sufficient amount of fluid is thenadded to the cement/barite blend to form a pumpable cementitious slurry.The fluid is preferably fresh water or salt water, i.e., an unsaturatedaqueous salt solution or a saturated aqueous salt solution such as brineor seawater. The amount of water introduced to the cement/barite blendmay vary but is a sufficient amount to provide a slurry and ispreferably selected to provide a cement slurry having a desired density.

As deemed appropriate by one skilled in the art, additional additivesmay be introduced to the cement for improving or changing itsproperties. Examples of such additives include, but are not limited to,set retarders (e.g., SCR-100L retarder, which is commercially availablefrom HES), fluid loss control additives (e.g., HALAD®-344 additive,which is commercially available from HES), defoamers (e.g., D-AIR 3000defoamer, which is commercially available from HES), crystalline silica(e.g., SSA-2 silica flour, which is commercially available from HES),dispersing agents, set accelerators, and formation conditioning agents.Other weighting materials known in the art may also be added to thecement in conjunction with the coarse barite. The additives can bepre-blended with the cement and the barite before the addition of afluid thereto. Alternatively, the additives can be introduced to thecement/barite blend concurrent with or after the addition of a fluidthereto.

In preferred embodiments, a well cementing process is performed usingthe cement slurry containing the coarse barite. The well cementingprocess includes drilling a well bore into a subterranean formationwhile circulating a drilling fluid through the well bore. A string ofpipe, e.g., casing, is then run in the well bore. The drilling fluid isconditioned by circulating it downwardly through the interior of thepipe and upwardly through the annulus, which is located between theexterior of the pipe and the walls of the well bore. The cement slurrycomprising coarse barite is then displaced down through the pipe and upthrough the annulus, where it is allowed to set into a hard mass. Inalternative embodiments, the cement slurry may be used for otherprojects such as well bore plugging, remedial cementing, and masonry orbuilding construction.

The presence of the coarse barite in the cement slurry provides severalbenefits. Having the ability to adjust the density of the slurry usingthe coarse barite ensures that the slurry can contain the hydrostaticpressures in the well bore. Due to the large average PSD of the coarsebarite, less surface area is available for wetting in the cement slurry.As a result, the rheology of the slurry is much lower than if the cementhad been mixed with a weighting agent having a smaller average PSD.Consequently, the cement slurry containing the coarse barite is easierto mix and experiences less friction during pumping than cement slurriescontaining conventional weighting materials.

It is also believed that the presence of the coarse barite in the cementslurry and the hardened cement formed therefrom favorably affects themechanical properties in those materials. For example, the addition ofthe coarse barite may favorably impact Poisson's ratio, Young's modulus,the tensile strength, the tensile fracture energy, the friction angle,and the cohesion of the set cement.

EXAMPLES

The invention having been generally described, the following examplesare given as particular embodiments of the invention and to demonstratethe practice and advantages hereof. It is understood that the examplesare given by way of illustration and are not intended to limit thespecification or the claims to follow in any manner.

The cement slurries formed in the examples were prepared and tested,with the exception of the thickening time test, according to the APIRecommended Practice, Specification 10B, 22^(nd) Edition, December 1997.

Example 1

A cement slurry containing SWEEP-WATE™ barite in accordance with thepresent invention was formed. The amounts of the components in thecement slurry are presented in Table 1. The density, yield, thickeningtime, compressive strength, and operating free water value for thecement slurry were measured. These measurements are also shown inTable 1. The cement slurry was sheared at several different rotationsper minute (RPM) to determine rheology data for the slurry at both 80°F. and 190° F. The rheology data was used to calculate the plasticviscosity and the yield point of the slurry, both of which are presentedin Table 2.

Comparative Example 1

The procedure of Example 1 was followed except that HI-DENSE®conventional hematite weighting material was substituted for the bariteweighting material. Also, a smaller amount of the HI-DENSE® material ascompared to the SWEEP-WATE™ barite was required to form the same slurrydensity. TABLE 1 Comparative Component Example 1 Example 1 Class Hcement 94 lbs 94 lbs SSA-2 crystalline silica 35% bwoc* 35% bwoc*HALAD ® 344 EXP fluid loss control 0.08 gal/sk* 0.08 gal/sk* agent D-AIR3000 defoamer 0.25% bwoc* 0.25% bwoc* SCR-100L set retarder 0.1 gal/sk*0.1 gal/sk* HI-DENSE ® No. 4 weighting material 20 lbs — SWEEP-WATE ™weighting material — 31 lbs Mixing water (fresh) 4.22 gal/sk* 4.57gal/sk* Slurry Density 18.4 lb/gal 18.4 lb/gal Slurry Yield 1.37 ft³/sk*1.43 ft³/sk* Thickening Time @ 219° F. & 14,600 3:32 (hr:min) 3:55(hr:min) psi Operating Free Water 0 mL 0 mL 12 Hour Compressive Strength@ 253° 2,480 psi 1,989 psi F. 24 Hour Compressive Strength @ 253° 2,950psi 2,730 psi F.*NOTE: bwoc = by weight of the cement; sk = sack

TABLE 2 Comparative Example 1 Example 1 Dial Dial Dial Dial RPM ReadingRPM Reading RPM Reading RPM Reading Rheology 600  600+ 30 60 600 468 3034 Data @ 80° F. 300 480 20 42 300 252 20 24 200 290 10 22 200 178 10 12100 172 6 14 100 96 6 8 60 110 3 8 60 62 3 4 PV* 450 YP* 15.7 PV* 240YP* 14.1 Rheology 600 402 30 30 600 198 30 16 Data @ 190° F. 300 224 2020 300 120 20 12 200 158 10 10 200 82 10 6 100  86 6 6 100 46 6 4 60  543 4 60 28 3 2 PV* 214 YP* 12.1 PV* 114 YP* 6NOTE:PV = plastic viscosity in centipoise units;YP = yield point in lbs/100 ft²

As shown in Table 1, the slurry containing the SWEEP-WATE™ barite(Example 1) exhibited a longer thickening time and a higher volumetricyield than the slurry containing HI-DENSE® material (Comparative Example1). In addition, the compressive strengths of the slurry containing theSWEEP-WATE™ barite were comparable to the compressive strengths of theslurry containing HI-DENSE® material, with the 24 hour compressivestrength being more similar than the 12 hour compressive strength.Further, as shown in Table 2, the actual RPM's (i.e., the dial readings)of the slurry containing SWEEP-WATE™ barite were lower than those of theslurry containing HI-DENSE® material. The plastic viscosity of theslurry containing SWEEP-WATE™ barite was also significantly less thanthat of the slurry containing HI-DENSE® material. Moreover, the yieldpoint of the slurry containing SWEEP-WATE™ barite was lower than that ofthe slurry containing HI-DENSE® material.

While the preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the invention. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Use of the term “optionally” with respect to any element of a claim isintended to mean that the subject element is required, or alternatively,is not required. Both alternatives are intended to be within the scopeof the claims.

Accordingly, the scope of protection is not limited by the descriptionset out above, but is only limited by the claims which follow, thatscope including all equivalents of the subject matter of the claims.Each and every claim is incorporated into the specification as anembodiment of the present invention. Thus, the claims are a furtherdescription and are an addition to the preferred embodiments of thepresent invention. The discussion of a reference in the Description ofRelated Art is not an admission that it is prior art to the presentinvention, especially any reference that may have a publication dateafter the priority date of this application. The disclosures of allpatents, patent applications, and publications cited herein are herebyincorporated by reference, to the extent that they provide exemplary,procedural or other details supplementary to those set forth herein.

1. A method of cementing in a subterranean formation comprising thesteps of: preparing a pumpable cement slurry comprising barite havingparticles with a particle size primarily greater than about 125 microns,wherein the cement slurry has a density in a range of from about 15lbs/gal to about 23 lbs/gal; pumping the slurry into the subterraneanformation; and allowing the slurry to set.
 2. The method of claim 1wherein said step of preparing the pumpable cement slurry comprisesblending the barite with a hydraulic cement.
 3. The method of claim 1wherein said step of preparing the pumpable cement slurry comprisesadding a sufficient amount of water to form the cement slurry.
 4. Themethod of claim 1 wherein about 90% of the particles are greater thanabout 125 microns in size.
 5. The method of claim 1 wherein the bariteis present in the cement slurry in an amount of about 5 to about 60weight % based on the total weight of cement therein.
 6. The method ofclaim 1 wherein the cement slurry further comprises at least one ofcrystalline silica, a fluid loss control agent, a retarding agent, and adefoamer.
 7. A method of cementing in a subterranean formationcomprising the steps of: preparing a cement composition comprisinghydraulic cement, water present in an amount sufficient to provide apumpable slurry, and barite, wherein the cement slurry has a density ina range of from about 15 lbs/gal to about 23 lbs/gal and wherein thebarite comprises particles about 90% of which are greater than about 125microns in size; pumping the slurry into the subterranean formation; andallowing the slurry to set.
 8. The method of claim 7 wherein the bariteis present in the cement slurry in an amount of about 5 to about 60weight % based on the total weight of cement therein.
 9. The method ofclaim 7 wherein the cement slurry further comprises at least one ofcrystalline silica, a fluid loss control agent, a retarding agent, and adefoamer.
 10. A process of preparing cement for use in a well borecomprising the step of introducing barite to the cement wherein thebarite comprises particles having a particle size primarily greater thanabout 125 microns and wherein a density of the cement slurry is in arange of from about 15 lbs/gal to about 23 lbs/gal.
 11. The process ofclaim 10 wherein about 90% of the particles is greater than about 125microns in size.
 12. The process of claim 10 wherein from about 5 toabout 100 weight % barite based on the total weight of the cement isintroduced to the cement.
 13. The process of claim 10 further comprisingthe step of mixing a fluid with the cement and the barite to form acement slurry.
 14. The process of claim 10 further comprising the stepof introducing at least one of crystalline silica, a fluid loss controlagent, a retarding agent, and a defoamer to the cement.
 15. A pumpablecement slurry comprising: a hydraulic cement; barite comprisingparticles having a particle size primarily greater than about 125microns; and water; wherein the cement slurry has a density in a rangeof from about 15 lbs/gal to about 23 lbs/gal.
 16. The cement compositionof claim 15 wherein about 90% of the particles is greater than about 125microns in size.
 17. The cement composition of claim 15 wherein thebarite is present in the cement composition in an amount of about 5 toabout 60 weight % based on the total weight of the cement.
 18. Thecement composition of claim 15 further comprising at least one ofcrystalline silica, a fluid loss control agent, a retarding agent, and adefoamer.